JP5001396B2 - Thermoelectric composition and method - Google Patents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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Description
本出願は、2005年6月6日に出願された仮出願第60/687769号の優先権を主張するものである。 This application claims the priority of provisional application 60/687769 for which it applied on June 6, 2005.
連邦政府の資金援助を受けた研究又は開発に関する申告:該当なし Declaration on federal-funded research or development: Not applicable
政府の権利に関する申告:該当なし Government rights declaration: Not applicable
本発明は、性能指数(ZT)を高めるナノスケールの内包物を有する、新規のバルク熱電組成物の製造方法に関する。特に、本発明は、ナノスケールの内包物を、透過型電子顕微鏡(TEM)画像化などの従来のナノスケール画像化技法によって見ることができる熱電組成物に関する。これらは発電用及びヒートポンプ用に有用である。 The present invention relates to a method for producing a novel bulk thermoelectric composition having nanoscale inclusions that increase the figure of merit (ZT). In particular, the present invention relates to thermoelectric compositions where nanoscale inclusions can be viewed by conventional nanoscale imaging techniques such as transmission electron microscopy (TEM) imaging. These are useful for power generation and heat pumps.
熱電材料及び素子における従来技術は、Cauchyの米国特許第5448109号、Kanatzidisらの米国特許第6312617号、並びにSterzelらの米国出願公開第2004/0200519 A1号及びKanatzidisらの同2005/0076944A1号に全般的に記載されている。これらの参考文献のそれぞれは、電気伝導度と熱電力の二乗との積を熱伝導度で割ったものに直接影響される性能指数(ZT)を増加させることに関する。一般的に、熱電材料の電気伝導度を増すと、熱伝導度も増加する。熱電素子の効率は、理論効率を下回り、商業的な目的に十分な効率にはなり得ない。 Prior art in thermoelectric materials and devices is generally described in Cauchy U.S. Pat. No. 5,448,109, Kanatzidis et al. U.S. Pat. No. 6,312,617, and Starzel et al. Has been described. Each of these references relates to increasing the figure of merit (ZT) that is directly affected by the product of electrical conductivity and the square of thermal power divided by thermal conductivity. In general, increasing the electrical conductivity of a thermoelectric material increases the thermal conductivity. The efficiency of thermoelectric elements is less than the theoretical efficiency and cannot be efficient enough for commercial purposes.
したがって、本発明の一目的は、比較的効率的なバルク熱電材料を提供することである。さらに、本発明の一目的は、これらの熱電材料の調製方法を提供することである。さらに、本発明の一目的は、人工的に蒸着された超格子薄膜熱電材料と比較して相対的に経済的に調製できる熱電材料を提供することである。これらの目的及び他の目的は、以下の説明及び図面によってさらに明らかとなるであろう。 Accordingly, one object of the present invention is to provide a relatively efficient bulk thermoelectric material. Furthermore, it is an object of the present invention to provide a method for preparing these thermoelectric materials. Furthermore, it is an object of the present invention to provide a thermoelectric material that can be prepared relatively economically compared to artificially deposited superlattice thin film thermoelectric materials. These and other objects will become more apparent from the following description and drawings.
本発明は、マトリックスを提供する第1のカルコゲニドの均質な固溶体又は化合物を、異なる組成を有する第2の相のナノスケール内包物と共に含み、組成物の性能指数(ZT)が内包物を含まない組成物の性能指数よりも大きい熱電組成物に関する。好ましくは、内包物は、組成物を、均質な固溶体の相図に基づいた融点よりも低い、ある適切な温度においてアニーリングした結果としてのスピノーダル分解によって形成されたものである。好ましくは、内包物は、マトリックスの溶融溶液をドーピングした結果としてのマトリックスカプセル化によって形成されたものである。好ましくは、内包物は、マトリックスの溶融溶液を冷却することによる内包物の核生成及び成長によって形成されたものである。 The present invention includes a homogeneous solid solution or compound of a first chalcogenide that provides a matrix, together with a second phase nanoscale inclusion having a different composition, and the figure of merit (ZT) of the composition does not include inclusions It relates to a thermoelectric composition that is larger than the figure of merit of the composition. Preferably, the inclusions are those formed by spinodal decomposition as a result of annealing the composition at some suitable temperature below the melting point based on the homogeneous solid solution phase diagram. Preferably, the inclusion is formed by matrix encapsulation as a result of doping with a molten solution of the matrix. Preferably, the inclusion is formed by nucleation and growth of the inclusion by cooling a molten solution of the matrix.
本発明はまた、少なくとも2つの異なる金属カルコゲニドのナノ粒子の均一な沈殿した分散物を含む、カルコゲニドの均一な固溶体又は化合物を含み、カルコゲンがテルル、イオウ及びセレンから成る群から選択される、熱電組成物にも関する。好ましくは、組成物は、固溶体のスピノーダル分解によって形成されたものである。 The present invention also includes a homogeneous solid solution or compound of chalcogenide, including a homogeneous precipitated dispersion of at least two different metal chalcogenide nanoparticles, wherein the chalcogen is selected from the group consisting of tellurium, sulfur and selenium. It also relates to a composition. Preferably, the composition is formed by spinodal decomposition of a solid solution.
本発明はまた、カルコゲニドの均質な固溶体又は化合物を、カルコゲニドに加えられた
金属又は半導体から得られる、分散したナノ粒子と共に含む熱電組成物にも関する。
The invention also relates to a thermoelectric composition comprising a homogeneous solid solution or compound of chalcogenide with dispersed nanoparticles obtained from a metal or semiconductor added to the chalcogenide.
本発明はまた、固溶体又は化合物とは異なる組成のナノ粒子の形成を可能にする温度でアニールされた、カルコゲニドの均質な固溶体又は化合物を含む熱電組成物にも関する。 The present invention also relates to a thermoelectric composition comprising a homogeneous solid solution or compound of chalcogenide that has been annealed at a temperature that allows the formation of nanoparticles of a different composition than the solid solution or compound.
本発明はさらに、内包物がマトリックスの溶融溶液をドーピングした結果、マトリックスカプセル化によって形成されたものである組成物に関する。 The invention further relates to a composition wherein the inclusion is formed by matrix encapsulation as a result of doping a molten solution of the matrix.
本発明はさらに、内包物がマトリックスの溶融溶液を冷却することによる内包物の核生成及び成長によって形成されたものである組成物に関する。 The invention further relates to a composition wherein the inclusion is formed by nucleation and growth of the inclusion by cooling a molten solution of the matrix.
本発明はさらに、以下のことを含む熱電組成物の調製方法に関する:
(a)第1のカルコゲニドの液体溶液又は液体化合物及び異なる組成を有する第2の相を形成させるステップ、
(b)溶液を急速に冷却するステップであって、マトリックスとしての第1のカルコゲニドの固溶体及びナノスケール内包物としての第2の相が形成され、その結果、性能指数が内包物を含まないものより大きいステップであって、好ましくは、内包物は、組成物を、均質な固溶体の相図に基づいた融点よりも低い、ある適切な温度においてアニーリングした結果としてのスピノーダル分解によって形成される。好ましくは、内包物は、マトリックスの溶融溶液を冷却することによるマトリックスカプセル化によって形成される。好ましくは、内包物は、マトリックスの過飽和固溶体における内包物の核生成及び成長によって形成される。好ましくは、カルコゲニドは、テルル、イオウ及びセレンから成る群から選択されるカルコゲンを有する。好ましくは、内包物は約1〜200ナノメートルである。
The present invention further relates to a method for preparing a thermoelectric composition comprising:
(A) forming a liquid solution or compound of the first chalcogenide and a second phase having a different composition;
(B) a step of rapidly cooling the solution, wherein a solid solution of the first chalcogenide as a matrix and a second phase as nanoscale inclusions are formed, so that the figure of merit does not include inclusions In a larger step, preferably the inclusion is formed by spinodal decomposition as a result of annealing the composition at some suitable temperature below the melting point based on the homogeneous solid solution phase diagram. Preferably, the inclusion is formed by matrix encapsulation by cooling a molten solution of the matrix. Preferably, the inclusion is formed by nucleation and growth of the inclusion in a supersaturated solid solution of the matrix. Preferably, the chalcogenide has a chalcogen selected from the group consisting of tellurium, sulfur and selenium. Preferably, the inclusion is about 1 to 200 nanometers.
本発明の物質及び利点は、以下の図面及び説明を参照することによって次第に明らかになるであろう。 The materials and advantages of the present invention will become increasingly apparent by reference to the following drawings and description.
ナノメートルサイズの内包物を含むバルク材料は、高められた熱電特性を提供する。熱電性能指数は、電気伝導度及びゼーベック指数を維持又は高めつつ、熱伝導度を低下させることによって向上する。マトリックス中のコヒーレントなナノメートルサイズの内包物は、フォノンの散乱サイトとして働き、これは続いて熱電導度を低下させる。これらの材料の調製の一般的方法が開発されてきた。
熱電式の熱を電気に変換する装置は、将来のエネルギーの保存、管理、及び利用において重要な役割を果たすことになる。熱電冷却器も、電子産業及び他の産業において重要な役割を果たしている。発電及び冷却用途における熱電材料の使用を拡大するためには、より効率的な熱電材料を特定する必要がある。
Bulk materials containing nanometer-sized inclusions provide enhanced thermoelectric properties. The thermoelectric figure of merit is improved by reducing the thermal conductivity while maintaining or increasing the electrical conductivity and Seebeck index. Coherent nanometer-sized inclusions in the matrix act as phonon scattering sites, which subsequently reduce the thermal conductivity. General methods for the preparation of these materials have been developed.
Devices that convert thermoelectric heat into electricity will play an important role in future energy storage, management, and utilization. Thermoelectric coolers also play an important role in the electronics industry and other industries. In order to expand the use of thermoelectric materials in power generation and cooling applications, it is necessary to identify more efficient thermoelectric materials.
先に指摘したとおり、熱電材料の品質を決定するために使用する尺度は、無次元の性能指数ZTであり、ZT=(σS2/κ)Tであり、σは電気伝導度であり、Sはゼーベック係数又は絶対熱電力であり、Tは温度であり、κは熱伝導度である。量σ・S2は電力因子と呼ばれる。このとき、目標は、同時に熱電力、電気伝導度(すなわち電力因子)を向上させ、且つ熱伝導度を低下させ、それによってZTを高めることである。前述の諸特性は密接に関係づけられている。 As pointed out above, the measure used to determine the quality of the thermoelectric material is the dimensionless figure of merit ZT, ZT = (σS 2 / κ) T, σ is the electrical conductivity, S Is the Seebeck coefficient or absolute thermal power, T is the temperature, and κ is the thermal conductivity. The quantity σ · S 2 is called the power factor. At this time, the goal is to simultaneously improve the thermal power and electrical conductivity (ie power factor) and reduce the thermal conductivity, thereby increasing ZT. The aforementioned characteristics are closely related.
PbTe及びSi/Ge合金は発電に使用されている最新の熱電材料である。これらの化合物は、ドープされると600K及び1200Kでそれぞれ約0.8の最大ZTを有する。これらの材料の熱伝導度を下げることによって、すでに知られている特性を犠牲にすることなく、ZTを向上させることができる。最近では、Bi2Te3並びにこれのBi2Se3及びSb2Te3との合金は、BiとSbの合金と共に熱電冷却材料としては最先端と見なされている。これらの材料はそれらの性能を最適化するために多くの方法で化学的に改良されているが、現在使用されている熱電材料の特性を高めるために顕著な改良を行うことができる。 PbTe and Si / Ge alloys are the latest thermoelectric materials used for power generation. These compounds, when doped, have a maximum ZT of about 0.8 at 600K and 1200K, respectively. By reducing the thermal conductivity of these materials, ZT can be improved without sacrificing the already known properties. Recently, Bi 2 Te 3 and its alloys with Bi 2 Se 3 and Sb 2 Te 3 are regarded as the most advanced thermoelectric cooling materials together with alloys of Bi and Sb. Although these materials have been chemically improved in many ways to optimize their performance, significant improvements can be made to enhance the properties of currently used thermoelectric materials.
熱電材料の効率を高めるためには、通常フォノンの散乱速度を上げると同時に高いキャリアー移動度を維持することが必要である。この点に関しては、薄膜超格子材料がZTを高めたことが実証されており、これは熱伝導度の低下によって説明することができる。超格子構造は、事実上、複合した構造界面の配置を作りだして、それが結果としてフォノン伝播の熱抵抗を高める。一方では、格子整合及び界面のコヒーレンスは、乱れのない電子の流れを確かにし、したがって高い移動度を維持する。電気伝導度と格子の熱伝導度のこの分離は、電気伝導度を犠牲にすることなく全体の熱伝導度を下げるために必要である。 In order to increase the efficiency of thermoelectric materials, it is usually necessary to increase the scattering speed of phonons and at the same time maintain a high carrier mobility. In this regard, it has been demonstrated that thin film superlattice materials have increased ZT, which can be explained by a decrease in thermal conductivity. The superlattice structure effectively creates a composite structural interface arrangement, which in turn increases the thermal resistance of phonon propagation. On the one hand, lattice matching and interfacial coherence ensure undisturbed electron flow and thus maintain high mobility. This separation of electrical conductivity and lattice thermal conductivity is necessary to reduce the overall thermal conductivity without sacrificing electrical conductivity.
超格子薄膜の難点は、調製が高価につき、成長が困難であり、材料全体にわたる大きな温度差を支えることが容易ではないことである。したがって、低価格で、製造が容易で、且つ温度勾配を容易に支えることができるバルク材料中へ、長さがナノメートルスケールの内包物を組み入れることが望ましい。 The disadvantages of superlattice thin films are that they are expensive to prepare, difficult to grow, and are not easy to support large temperature differences across the material. Therefore, it is desirable to incorporate nanometer-scale inclusions into bulk materials that are inexpensive, easy to manufacture, and can easily support temperature gradients.
本発明で、熱電材料作製のための所望のナノ複合材料の製造においては3つの方法が使用された。これらの方法のそれぞれを、以下のセクションで、実施例、透過型電子顕微鏡(TEM)画像、及びそれぞれの一般的方法から作製することができる材料系の表と一緒に詳細に考察する。第1の、スピノーダル分解は、ナノメートル長さのスケールにおいて組成のゆらぎを有する材料を作るために使用した。他の2つの方法、マトリックスカプセル化並びに核生成及び成長は、ホストマトリックスの内部で、さまざまな材料の内包物を生成する能力を示した。 In the present invention, three methods were used in the production of the desired nanocomposite material for thermoelectric material fabrication. Each of these methods is discussed in detail in the following sections, along with examples, transmission electron microscope (TEM) images, and tables of material systems that can be made from each general method. The first, spinodal decomposition, was used to make a material with compositional fluctuations on a nanometer length scale. Two other methods, matrix encapsulation and nucleation and growth, showed the ability to produce inclusions of various materials within the host matrix.
半導体結晶中のフォノンの平均自由行程、tphは、1≦tph≦100nmの範囲内にあり、温度の上昇につれて減少する傾向がある。ナノ複合熱電材料の実現は、フォノン散乱によって格子熱伝導度を大幅に抑えることができるナノメートルサイズの散乱体を導入する手段を提供する。広い粒子サイズ分布の存在は、フォノンスペクトルのより広い範囲での散乱の可能性を提供する。 The mean free path of phonons in the semiconductor crystal, t ph, is in the range of 1 ≦ t ph ≦ 100 nm and tends to decrease with increasing temperature. The realization of nanocomposite thermoelectric materials provides a means to introduce nanometer-sized scatterers that can significantly reduce lattice thermal conductivity by phonon scattering. The presence of a broad particle size distribution offers the possibility of scattering over a wider range of the phonon spectrum.
室温以下での上記のことの実験による確認は、図1に示す格子熱伝導度のプロットのようにPbTe−PbS16% at.系から得られ、ナノ沈殿試料の場合には、室温において同じ組成の完全混合物に対して、格子熱伝導度の>40%の低下が観察される。 Confirmation by the experiment of the above at room temperature or less is as follows. PbTe-PbS 16% at. In the case of nanoprecipitated samples obtained from the system, a> 40% decrease in lattice thermal conductivity is observed for a complete mixture of the same composition at room temperature.
バンドギャップエンジニアリング又は電子のエネルギー状態のエンジニアリングは、熱電材料の電力因子をさらに高めるための別の手段を提供することが示唆されてきた。基本的には、着想は放物線バンド(バルク半導体)と次元性の低下した構造(すなわちナノドットが櫛状の状態密度を示す)を混合して、複合材料の得られる状態密度に対する波及効果を出現させることにある。 Band gap engineering or electronic energy state engineering has been suggested to provide another means to further increase the power factor of thermoelectric materials. Basically, the idea is to mix a parabolic band (bulk semiconductor) and a structure with reduced dimensionality (ie, nanodots show a comb-like density of states) to produce a ripple effect on the resulting density of states of the composite material. There is.
高められた電力因子の実験による確認は、以下の表1に示す系から得られる:
方法1:スピノーダル分解
スピノーダル分解とは、2相からなる安定な1相混合物を不安定にすることができる方法のことである。熱力学的には、不均一相が安定性又は準安定性のための必要条件は、ある成分の化学ポテンシャルがその成分の濃度の増加と共に増加しなければならないということである。2成分については、この条件は、
に帰し、Xは濃度である。この条件が満たされない場合は、混合物は連続的な組成変化に対して不安定であり、この準安定性の限度はスピノーダルと呼ばれて、
で定義され、Xは濃度である。混合相系の両成分は同じ格子を共有しているので、スピノーダルなゆらぎには、結晶転換は関与せず、ナノスケールでの局所的組成の空間的変化が関与する。この空間的変化は、熱電マトリックス中にコヒーレントに埋め込まれたある相のナノ粒子を作るために、したがって大きな反応規模でナノ構造の熱電材料を作るために利用された。
Method 1: Spinodal decomposition Spinodal decomposition is a method capable of destabilizing a stable one-phase mixture composed of two phases. Thermodynamically, a prerequisite for the stability or metastability of a heterogeneous phase is that the chemical potential of a component must increase with increasing concentration of that component. For two components, this condition is
, X is the concentration. If this condition is not met, the mixture is unstable to continuous composition changes, and this metastability limit is called spinodal,
Where X is the concentration. Since both components of the mixed phase system share the same lattice, spinodal fluctuations do not involve crystal transformation and involve spatial changes in local composition at the nanoscale. This spatial change has been exploited to create a phase of nanoparticles coherently embedded in a thermoelectric matrix and thus to produce nanostructured thermoelectric materials on a large reaction scale.
混合性に隙間のある相図、すなわち等圧又は等温相図の共存曲線内の少なくとも2相が共存する領域を考える(図2Aを参照されたい)。相A及び相Bと組成X0との混合物が高温T1で処理され、次いでより低い温度T2までクエンチされる溶液である場合は、直後には組成はいたるところで同じ(理想的な固溶体)であり、よって、系の自由エネルギーはG(X)曲線上のG0であろう。しかし、無限小の組成の揺らぎが原因で、系は局所的にAリッチな領域及びBリッチな領域を生じる。このとき、系は全自由エネルギーが減少しているので、不安定になっている。時間と共に、系は系全体が平衡組成X1及びX2に到達するまで分解する(図2A及び図2Bを比較されたい)。 Consider a region in which at least two phases coexist in a coexistence curve of a phase diagram with a gap in mixing, ie, an isobaric or isothermal phase diagram (see FIG. 2A). Phase mixture of A and phase B with composition X 0 is treated at a high temperature T 1, then if a solution is quenched to a lower temperature T 2, the same at composition throughout immediately after (ideal solid solution) Thus, the free energy of the system will be G 0 on the G (X) curve. However, due to infinitesimal compositional fluctuations, the system produces locally A-rich and B-rich regions. At this time, the system is unstable because the total free energy is decreasing. Over time, the system decomposes until the entire system reaches equilibrium compositions X 1 and X 2 (compare FIGS. 2A and 2B).
熱電ナノ複合材料を製造するために、スピノーダル分解法を適用することには次の2つの主要な利点がある;(a)熱力学の原理は、空間的変化の波長λが、大いに望ましいフォノンの散乱長のスケールである、2≦λ≦5nmの範囲内であると規定していること、及び(b)ナノ構造が熱力学的に安定であること。したがって、スピノーダル分解された熱電材料は、相図によって規定される特定の温度領域で使用する場合には永続的に安定な、自然生成バルクナノ複合材料である。 There are two major advantages to applying the spinodal decomposition method to produce thermoelectric nanocomposites: (a) The principle of thermodynamics is that the wavelength λ of spatial variation is highly desirable for phonons It stipulates that it is within the range of 2 ≦ λ ≦ 5 nm, which is the scale of the scattering length, and (b) the nanostructure is thermodynamically stable. Thus, spinodal decomposed thermoelectric materials are naturally produced bulk nanocomposites that are permanently stable when used in the specific temperature range defined by the phase diagram.
前述の手順は、PbTeがマトリックスとして働くPbTe−PbS系において広く適用された。 The above procedure has been widely applied in the PbTe-PbS system where PbTe acts as a matrix.
PbTe−PbS x%調製の実施例:
PbTe−PbS x%2成分系のスピノーダル分解は、−4≦x≦96%については約700℃未満の温度で起こる(添付の図3の相図を参照されたい)。高純度の出発材料を、王水で清浄化した溶融シリカ管中で混合してから、図3Bに示す反応プロファイルに従って焼く。
Example of preparation of PbTe-PbS x%:
Spinodal decomposition of the PbTe-PbS x% binary system occurs at temperatures below about 700 ° C. for -4 ≦ x ≦ 96% (see attached phase diagram in FIG. 3). High purity starting materials are mixed in fused silica tubes cleaned with aqua regia and then baked according to the reaction profile shown in FIG. 3B.
スピノーダル分解したPbTe−PbS 16%系のTEM画像を、図3C、3Dに示す。 A TEM image of the spinodal decomposed PbTe-PbS 16% system is shown in FIGS. 3C and 3D.
以下の表2は、スピノーダル分解機序によってナノ構造状態で存在するように製造することができる系を示す。ここに挙げたものは、A1−xBxの化学量諭比(0<x<1)の成分A及びBから構成される一組の材料である。
方法2:マトリックスカプセル化
これらの系は、相図によって表されているように、少量相が約0.1〜15%の組成範囲で組成物中の固溶体を有していなければならない。しかし、これらの系は、溶融物からクエンチされた場合に、少量相材料のナノメートルスケールでの内包物を示すことが観察された。この現象は、マトリックスが良好な熱電性であり、少量相は反応性がなく、より低い融点を有し、且つ液体状態でマトリックスと可溶な材料である、熱電的な関心のある他の系に拡大することができる。少量相はまた、それ自身が化合物を形成することができるか又はできない、これらの反応性のない材料の2つ以上の混合物であってもよい。これらの材料は、少量相を凍結させるために、マトリックスの融点を通過して速やかにクエンチしなければならない。クエンチした後は、サンプルを後アニールして、結晶性及び熱電特性を向上させなければならない。
実施例:この方法をPbTe−Sb、PbTe−Bi、PbTe−InSb及びPbTe−Pb−Sbに適用し、それぞれの事例で有望であることを示した。
Method 2: Matrix Encapsulation These systems must have a solid solution in the composition in the composition range of about 0.1-15% of the minor phase, as represented by the phase diagram. However, these systems were observed to exhibit inclusions on the nanometer scale of minor phase materials when quenched from the melt. This phenomenon is due to other systems of thermoelectric interest where the matrix is a good thermoelectric, the minor phase is not reactive, has a lower melting point, and is a material that is soluble with the matrix in the liquid state. Can be expanded. The minor phase may also be a mixture of two or more of these non-reactive materials, which themselves may or may not form a compound. These materials must be rapidly quenched through the melting point of the matrix to freeze the small phase. After quenching, the sample must be post-annealed to improve crystallinity and thermoelectric properties.
Examples: This method was applied to PbTe-Sb, PbTe-Bi, PbTe-InSb and PbTe-Pb-Sb, and showed promise in each case.
PbTe−Sb 4%調製の実施例
テルル化鉛及びアンチモニーを適切なモル比で組み合わせて、真空にした溶融シリカの管に封入し、図4Bに示すプロファイルに従って加熱した。明視野画像及び暗視野画像を図4C〜4Eに示す。カプセル化されたナノ粒子のTEM画像を、図4F〜4Kに示す。図4Lは、格子熱伝導度を示す。
Example of PbTe-Sb 4% Preparation Lead telluride and antimony were combined in appropriate molar ratios, sealed in a vacuumed fused silica tube and heated according to the profile shown in FIG. 4B. Bright field images and dark field images are shown in FIGS. TEM images of the encapsulated nanoparticles are shown in FIGS. FIG. 4L shows the lattice thermal conductivity.
表3は、マトリックスカプセル化用の系を、マトリックス及び沈殿物を一覧表にして、示している。 Table 3 shows the system for matrix encapsulation, listing the matrix and precipitates.
2種類以上のナノ相粒子を使用するマトリックスカプセル化:複数のナノスケール内包物(表3に上げられているものから2つ以上)を有するサンプルを、マトリックスカプセル化法によって作ることができる。 Matrix encapsulation using two or more types of nanophase particles: Samples with multiple nanoscale inclusions (two or more from those listed in Table 3) can be made by matrix encapsulation methods.
これらの内包物は、それぞれの好ましい特性を組み合わせて、優れた熱電材料を製造するために使用する。追加される相はまた、液体状態でマトリックスと可溶でなければならず、マトリックスと反応性であってもなくてもよく、互いの間で化合物を形成してもしなくてもよい。この方法は、熱伝導度の低下という点でも、また電気輸送の挙動の改良という点でも興味深い挙動を示すSb及びPbの両方の内包物を有するPbTeに対して適用されてきた。PbとSbの比は、より高い電気伝導度が所望の温度範囲を通じて維持されるように伝導度を改良することができる。追加された相に付随する質量のゆらぎが、先に考察した実施例で見られるように、熱伝導度を低下させる。 These inclusions are used to produce excellent thermoelectric materials by combining the preferred properties of each. The added phase must also be soluble with the matrix in the liquid state, may or may not be reactive with the matrix, and may or may not form a compound between each other. This method has been applied to PbTe with both Sb and Pb inclusions that exhibit interesting behavior both in terms of reduced thermal conductivity and in terms of improved electrotransport behavior. The ratio of Pb and Sb can improve the conductivity so that a higher electrical conductivity is maintained throughout the desired temperature range. The mass fluctuation associated with the added phase reduces the thermal conductivity, as seen in the examples discussed above.
PbTe−Pb−Sb調製の実施例
Pb、Sb、及びTeは、真空にした溶融シリカ管中に封入して、溶融状態まで加熱した。次いで、管を溶融物の急冷のために高温炉から取り出した。この手順は上で論じたものと同様であるが、単一成分の内包物ではなく、複数のナノ沈殿物の内包物相を使用した。多くのさまざまな使用可能な内包物の組合せがありうるが、一例のPbTe−Pb−Sbを下に示す。
Example of PbTe-Pb-Sb preparation Pb, Sb, and Te were encapsulated in a vacuumed fused silica tube and heated to a molten state. The tube was then removed from the high temperature furnace for quenching of the melt. The procedure is similar to that discussed above, but with multiple nanoprecipitate inclusion phases rather than single component inclusions. There are many different possible inclusion combinations, but an example PbTe-Pb-Sb is shown below.
SEM顕微鏡写真(図5A及び5B)、粉末X線回折(図6A及び6B)、TEM顕微鏡写真(図7A及び7B)、並びに実験的電力因子及び熱伝導度値(図8)。これらの系は、内包物相の全濃度、さまざまな内包物相の比率、及び内包物自体の特性などのいくつかの変数によって輸送特性を調節することができる興味深い材料の組である。最適化はまだ行われているところであるが、すでに調製されたままの系で1を超えるZT値が得られている。
方法3:核生成及び成長機序
熱電材料のマトリックス内部でのナノ粒子の核生成及び成長の方法は、複合材料の相図に決定的に依存する3つの異なる熱処理から成る。
a)(適切な化学量論比で混合された)出発材料を、相図の2相領域から1相領域まで加熱して、すべての沈殿物を溶解させる。混合物をそこで数時間保ち、完全な均一性を確実にする。
b)溶融物又は固溶体を、さまざまな方法(空気クエンチ、水クエンチ、氷クエンチ)を使用して、室温までクエンチする。これは高温の均一相を凍結して過飽和固溶体にする。c)個々の系の動力学に応じて、試料を相図の2相領域内の高められた温度で後アニールし、そこで数時間保持して、ナノ沈殿物を形成させ成長させる。アニールする時間及び温度は沈殿物のサイズの成長と比例する。したがって、アニールする時間及び温度の注意深い選択によってナノ沈殿物のサイズを制御することができる。
Method 3: Nucleation and Growth Mechanism The method of nucleation and growth of nanoparticles within the matrix of thermoelectric material consists of three different heat treatments that depend critically on the phase diagram of the composite material.
a) The starting material (mixed at the appropriate stoichiometric ratio) is heated from the two-phase region to the one-phase region of the phase diagram to dissolve all precipitates. The mixture is kept there for several hours to ensure complete uniformity.
b) The melt or solid solution is quenched to room temperature using various methods (air quench, water quench, ice quench). This freezes the hot homogeneous phase into a supersaturated solid solution. c) Depending on the dynamics of the individual system, the sample is post-annealed at an elevated temperature within the two-phase region of the phase diagram where it is held for several hours to form and grow a nanoprecipitate. The annealing time and temperature are proportional to the size growth of the precipitate. Thus, the size of the nanoprecipitate can be controlled by careful selection of annealing time and temperature.
以下の略図は、図9A、9B及び9Cにおいて、第2の相のナノ沈殿が起こる様子を大ざっぱに示している。 The following schematic diagram schematically shows how the second phase nanoprecipitation occurs in FIGS. 9A, 9B and 9C.
一般則として、この種のナノ構造を有する熱電材料は2つの条件を満たさなければならない:(1)2つの相は、特定の温度においては固溶体相に入り、他のより低い温度においては混合物中へ分離する元素を含有しなければならない。(2)沈殿分離する相はコヒーレント又は最良にはセミコヒーレントな沈殿物を創らなければならない。コヒーレントであることは、それがマトリックス格子との結合を確実にし、それ故に沈殿物は電子に対する強い散乱体としては働かないので重要である。 As a general rule, a thermoelectric material with this type of nanostructure must satisfy two conditions: (1) the two phases enter the solid solution phase at a certain temperature and in the mixture at other lower temperatures It must contain elements that separate into (2) Precipitate The phase to be separated must create a coherent or best semi-coherent precipitate. Being coherent is important because it ensures bonding with the matrix lattice and therefore the precipitate does not act as a strong scatterer for electrons.
上記の手順は、PbTe−CdTe系に対して幅広く適用されて、優れた結果が得られている。 The above procedure has been widely applied to the PbTe-CdTe system with excellent results.
実施例
PbTe−CdTe x%調製の実施例
2≦x≦9のx%を目標にして化学量論量のPb、Te及びCdを秤量する。出発材料をグラファイトのるつぼに入れ、続いて高真空下でシリカ管中に封入してから、後に示す反応プロファイル(図9E)に従って焼く。この反応プロファイルはPbTe−CdTe系の相図(図9D)に基づいて決定されている。図9F及び9Gは、PbS−PbTe 6%の沈殿及び成長に関するTEM画像を示す。図9H及び9Iは、PbTe−CdTe
9%系を示す。
Example PbTe-CdTe x% Preparation Example Stoichiometric amounts of Pb, Te and Cd are weighed to target x% of 2 ≦ x ≦ 9. The starting material is placed in a graphite crucible and subsequently encapsulated in a silica tube under high vacuum and then baked according to the reaction profile shown below (FIG. 9E). This reaction profile is determined based on the phase diagram of the PbTe-CdTe system (FIG. 9D). FIGS. 9F and 9G show TEM images for PbS-PbTe 6% precipitation and growth. 9H and 9I show PbTe-CdTe
9% system is shown.
以下の表4は、核生成及び成長用の系を、マトリックス及び沈殿物を列挙して、示している。
先の説明は、本発明の例示するものに過ぎず、且つ本発明は添付の特許請求の範囲によってのみ限定されるものとする。 The foregoing description is merely illustrative of the invention and the invention is limited only by the scope of the appended claims.
Claims (28)
前記ナノスケール内包物は、前記マトリックスを有するコヒーレント又はセミコヒーレントで、前記第1のカルコゲニドとは異なる組成物を有するものであり、その結果、前記ナノスケール内包物は、前記組成物の電気伝導性及びゼーベック係数を実質的に維持又は増加させながら、前記組成物中のフォノンを散乱させることによって前記組成物の熱伝導性を減少させる、前記熱電組成物。 A thermoelectric composition comprising a matrix comprising a first chalcogenide and nanoscale inclusions in the matrix,
The nanoscale inclusions are coherent or semicoherent with the matrix and have a composition different from the first chalcogenide, so that the nanoscale inclusions are electrically conductive of the composition. And the thermoelectric composition that reduces the thermal conductivity of the composition by scattering phonons in the composition while substantially maintaining or increasing the Seebeck coefficient.
前記ナノスケール内包物は第1の融点を有し、前記マトリックスは第2の融点を有し、前記第1の融点は前記第2の融点よりも低く、前記ナノスケール内包物は前記第1のカルコゲニドとは異なる組成物を有し、その結果、前記ナノスケール内包物は、前記組成物の電気伝導性及びゼーベック係数を実質的に維持又は増加させながら、前記組成物中のフォノンを散乱させることによって前記組成物の熱伝導性を減少させる、前記熱電組成物。 A thermoelectric composition comprising a matrix comprising a first chalcogenide and nanoscale inclusions in the matrix,
The nanoscale inclusion has a first melting point, the matrix has a second melting point, the first melting point is lower than the second melting point, and the nanoscale inclusion is the first melting point. Having a composition different from chalcogenide, so that the nanoscale inclusions scatter phonons in the composition while substantially maintaining or increasing the electrical conductivity and Seebeck coefficient of the composition Said thermoelectric composition, which reduces the thermal conductivity of said composition.
前記ナノスケール内包物は前記第1のカルコゲニドとは異なる第2のカルコゲニドを含み、前記第2のカルコゲニドはテルル、硫黄及びセレンからなる群から選択されるカルコゲンを含み、その結果、前記ナノスケール内包物は、50ナノメートル未満の大きさであって、前記組成物の電気伝導性及びゼーベック係数を実質的に維持又は増加させながら、前記組成物中のフォノンを散乱させることによって前記組成物の熱伝導性を減少させる、前記熱電組成物。 A thermoelectric composition comprising a matrix comprising a first chalcogenide and nanoscale inclusions in the matrix,
The nanoscale inclusion includes a second chalcogenide different from the first chalcogenide, and the second chalcogenide includes a chalcogen selected from the group consisting of tellurium, sulfur and selenium, and as a result, the nanoscale inclusion. The object has a size of less than 50 nanometers and scatters the phonons in the composition while substantially maintaining or increasing the electrical conductivity and Seebeck coefficient of the composition. The thermoelectric composition that reduces conductivity.
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KR101840202B1 (en) | 2016-08-22 | 2018-03-20 | 엘지전자 주식회사 | Thermoelectric material utilizing supper lattice material and thermoelectric device using the same |
US11223002B2 (en) | 2016-08-22 | 2022-01-11 | Lg Electronics Inc. | Superlattice thermoelectric material and thermoelectric device using same |
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JP4917091B2 (en) | 2012-04-18 |
WO2006133031A3 (en) | 2007-12-13 |
CA2609596A1 (en) | 2006-12-14 |
BRPI0610888A2 (en) | 2010-08-03 |
JP2010212699A (en) | 2010-09-24 |
US7847179B2 (en) | 2010-12-07 |
EP1889304A4 (en) | 2011-08-10 |
US20060272697A1 (en) | 2006-12-07 |
CA2609596C (en) | 2016-07-26 |
CN101189742A (en) | 2008-05-28 |
WO2006133031A2 (en) | 2006-12-14 |
JP2008543110A (en) | 2008-11-27 |
EP1889304A2 (en) | 2008-02-20 |
US20110042607A1 (en) | 2011-02-24 |
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